16547-11-8

Upstream product

• 622-95-7 4-chlorobenzyl bromide 
• 100-61-8 N-methylaniline 
• 104-83-6 1-Chloro-4-(chloromethyl)benzene 
• 64-18-6 formic acid 
• 2362-79-0 N-(4-chlorobenzylidene)aniline 
• 1517-46-0 4-chloro-N-methyl-N-phenyl-benzamide 
• 637-87-6 1-Chloro-4-iodobenzene 
• 121-69-7 N,N-dimethyl-aniline 
• 61821-46-3 4-chloro-N-methyl-N-phenylbenzothioamide 
• 104-88-1 4-chlorobenzaldehyde 

Downstream Products

• 1262227-16-6 methyl 2-(4-(4-chlorobenzyl(methyl)amino)phenyl)-2-phenylacetate 

Relevant academic research and scientific papers

BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant

A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.

Regioselective, Photocatalytic α-Functionalization of Amines

Photocatalytic α-functionalization of amines provides a mild and atom-economical means to synthesize α-branched amines. Prior examples featured symmetrical or electronically biased substrates. Here we report a controllable α-functionalization of amines in which regioselectivity can be tuned with minor changes to the reaction conditions.

Ru-Catalyzed Deoxygenative Transfer Hydrogenation of Amides to Amines with Formic Acid/Triethylamine

A ruthenium(II)-catalyzed deoxygenative transfer hydrogenation of amides to amines using HCO2H/NEt3 as the reducing agent is reported for the first time. The catalyst system consisting of [Ru(2-methylallyl)2(COD)], 1,1,1-tris(diphenylphosphinomethyl) ethane (triphos) and Bis(trifluoromethane sulfonimide) (HNTf2) performed well for deoxygenative reduction of various secondary and tertiary amides into the corresponding amines in high yields with excellent selectivities, and exhibits high tolerance toward functional groups including those that are reduction-sensitive. The choice of hydrogen source and acid co-catalyst is critical for catalysis. Mechanistic studies suggest that the reductive amination of the in situ generated alcohol and amine via borrowing hydrogen is the dominant pathway. (Figure presented.).

B(C6F5)3-Catalyzed Deoxygenative Reduction of Amides to Amines with Ammonia Borane

The first B(C6F5)3-catalyzed deoxygenative reduction of amides into the corresponding amines with readily accessible and stable ammonia borane (AB) as a reducing agent under mild reaction conditions is reported. This metal-free protocol provides facile access to a wide range of structurally diverse amine products in good to excellent yields, and various functional groups including those that are reduction-sensitive were well tolerated. This new method is also applicable to chiral amide substrates without erosion of the enantiomeric purity. The role of BF3 ? OEt2 co-catalyst in this reaction is to activate the amide carbonyl group via the in situ formation of an amide-boron adduct. (Figure presented.).

2-Aminoquinazolin-4(3H)-one as an Organocatalyst for the Synthesis of Tertiary Amines

The potential of 2-aminoquinazolin-4(3H)-one as an organocatalyst for the activation of aldehydes via noncovalent interaction for the synthesis of tertiary amines using formic acid as a reducing agent is reported for the first time. The developed protocol demonstrated a dilated substrate scope for aromatic and aliphatic amines with aromatic and aliphatic aldehydes. Furthermore, the current method was also fruitful for the derivatization of ciprofloxacin and its derivative in good to excellent yields.

Preparation method by using amine and imine nitrogen methylation and application thereof

The invention discloses a preparation method by using amine and imine nitrogen methylation and application thereof. The preparation method comprises the following steps: A, adding an active carbon loaded platinum catalyst into a Schlenk tube, and after vacuumizing to replace argon, adding a solvent; B, under protection of argon, separately adding phenylsilane, an initial raw material and formic acid; C, stirring the whole reaction system at a certain temperature to react; and D, after reaction, adding ethyl acetate into the system to dilute, stopping the reaction by using a sodium hydroxide aqueous solution, performing extraction with ethyl acetate, separating out an organic phase, drying and filtering the organic phase, and performing rotatable evaporation to remove the solvent. Column chromatography is performed on residues by using ethyl acetate/petroleum ether mixed solvent to obtain a target product, wherein the ethyl acetate and petroleum ether are different in proportion. According to the application of the method in isotope labeled drug synthesis, the dosage of a catalyst is extremely low, the cost is quite low, and the method is suitable for large-scaled production, can be suitable for amine and imine with different substituents, and suitable for realizing methylation conveniently on nitrogen atoms in a natural product structure to prepare drug molecules.

General Reductive Amination of Aldehydes and Ketones with Amines and Nitroaromatics under H2 by Recyclable Iridium Catalysts

Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaromatics and amines using H2. The iridium catalysts were prepared by pyrolysis of ionic liquid 1-methyl-3-cyanomethylimidazoulium chloride ([MCNI]Cl) with iridium chloride (IrCl3) in activated carbons. Iridium particles were well dispersed and stable in the N-doped carbon materials from [MCNI]Cl with activated carbon. The Ir@NC(600-2h) catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H2 and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC(600-2h) catalyst can be reusable several times without evident deactivation.

Methylation of aromatic amines and imines using formic acid over a heterogeneous Pt/C catalyst

We describe here a commercially available Pt/C catalyst capable of catalyzing the methylation of anilines and aromatic imines with formic acid in the presence of a hydrosilane reductant. Both primary aniline and secondary aniline can be methylated. The advantage of this newly described method includes operational simplicity, high TON, ready availability of the catalyst, and also good functional group compatibility.

Heterogeneous cobalt catalysts for reductive amination with H2: General synthesis of secondary and tertiary amines

Heterogeneous Co@NC catalysts were prepared, characterized and applied for the reductive amination of aldehydes and ketones with H2 gas. The Co catalyst Co@NC (800-2 h) was found to be active and selective for the reductive amination of aldehydes and ketones using H2 gas. Thus, general synthesis of secondary and tertiary amines was developed by the Co-catalyzed reductive amination with H2 gas, and various secondary and tertiary amines can be obtained in high yields. Moreover, a practical synthesis of N-substituted isoindolinones was also presented by a one step process with the Co@NC (800-2 h) catalyst. The Co@NC (800-2 h) catalyst is reusable at least five times without evident loss of activity.

Chemoselective reductive amination of carbonyl compounds for the synthesis of tertiary amines using SnCl2·2H2O/PMHS/MeOH

Stannous chloride catalyzed chemoselective reductive amination of a variety of carbonyl compounds with aromatic amines has been developed for the synthesis of a diverse range of tertiary amines using inexpensive polymethylhydrosiloxane as reducing agent in methanol. The present method is also applicable for the synthesis of secondary amines including heterocyclic ones.